biostudies-literatureHeller JAustrian Science Fund FWFBundesministerium für Bildung, Wissenschaft und Forschung14699-14708https://www.ebi.ac.uk/biostudies/studies/S-EPMC9215701biostudies-literatureUnknown24(24)Infrared spectra of the hydrated vanadium cation (V⁺(H₂O)_<i>n</i>; <i>n</i> = 3-51) were measured in the O-H stretching region employing infrared multiple photon dissociation (IRMPD) spectroscopy. Spectral fingerprints, along with size-dependent fragmentation channels, were observed and rationalized by comparing to spectra simulated using density functional theory. Photodissociation leading to water loss was found for cluster sizes <i>n</i> = 3-7, consistent with isomers featuring intact water ligands. Loss of molecular hydrogen was observed as a weak channel starting at <i>n</i> = 8, indicating the advent of inserted isomers, HVOH⁺(H₂O)_<i>n</i>-1. The majority of ions for <i>n</i> = 8, however, are composed of two-dimensional intact isomers, concordant with previous infrared studies on hydrated vanadium. A third channel, loss of atomic hydrogen, is observed weakly for <i>n</i> = 9-11, coinciding with the point at which the H and H₂O calculated binding energies become energetically competitive for intact isomers. A clear and sudden spectral pattern and fragmentation channel intensity at <i>n</i> = 12 suggest a structural change to inserted isomers. The H₂ channel intensity decreases sharply and is not observed for <i>n</i> = 20 and 25-51. IRMPD spectra for clusters sizes <i>n</i> = 15-51 are qualitatively similar indicating no significant structural changes, and are thought to be composed of inserted isomers, consistent with recent electronic spectroscopy experiments.Physical chemistry chemical physics : PCCPSize-dependent H and H₂ formation by infrared multiple photon dissociation spectroscopy of hydrated vanadium cations, V⁺(H₂O)_<i>n</i>, <i>n</i> = 3-51.PMC9215701P29174Innsbruck Laser Core FacilityW1259-N27P 29174Cunningham EMHeller Jvan der Linde COncak MBeyer MKHartmann JCfalseSize-dependent H and H₂ formation by infrared multiple photon dissociation spectroscopy of hydrated vanadium cations, V⁺(H₂O)_<i>n</i>, <i>n</i> = 3-51.Infrared spectra of the hydrated vanadium cation (V⁺(H₂O)_<i>n</i>; <i>n</i> = 3-51) were measured in the O-H stretching region employing infrared multiple photon dissociation (IRMPD) spectroscopy. Spectral fingerprints, along with size-dependent fragmentation channels, were observed and rationalized by comparing to spectra simulated using density functional theory. Photodissociation leading to water loss was found for cluster sizes <i>n</i> = 3-7, consistent with isomers featuring intact water ligands. Loss of molecular hydrogen was observed as a weak channel starting at <i>n</i> = 8, indicating the advent of inserted isomers, HVOH⁺(H₂O)_<i>n</i>-1. The majority of ions for <i>n</i> = 8, however, are composed of two-dimensional intact isomers, concordant with previous infrared studies on hydrated vanadium. A third channel, loss of atomic hydrogen, is observed weakly for <i>n</i> = 9-11, coinciding with the point at which the H and H₂O calculated binding energies become energetically competitive for intact isomers. A clear and sudden spectral pattern and fragmentation channel intensity at <i>n</i> = 12 suggest a structural change to inserted isomers. The H₂ channel intensity decreases sharply and is not observed for <i>n</i> = 20 and 25-51. IRMPD spectra for clusters sizes <i>n</i> = 15-51 are qualitatively similar indicating no significant structural changes, and are thought to be composed of inserted isomers, consistent with recent electronic spectroscopy experiments.2022-01-01T00:00:00Z2022 Jun2024-10-16T07:14:48.453Z2022-07-23T12:20:17.82ZS-EPMC92157013543810010.1039/d2cp00833e